CN107275700B - A kind of waste and old lithium ion battery recovery and treatment method being crushed based on wet type - Google Patents
A kind of waste and old lithium ion battery recovery and treatment method being crushed based on wet type Download PDFInfo
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- CN107275700B CN107275700B CN201610214115.XA CN201610214115A CN107275700B CN 107275700 B CN107275700 B CN 107275700B CN 201610214115 A CN201610214115 A CN 201610214115A CN 107275700 B CN107275700 B CN 107275700B
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The present invention provides a kind of waste and old lithium ion battery recovery method being crushed based on wet type, and described method includes following steps: waste and old lithium ion battery carries out discharge treatment；It carries out wet type to the waste and old lithium ion battery after electric discharge to be crushed, the broken solvent used of the wet type is organic solvent；The solidliquid mixture obtained after broken to wet type is separated by solid-liquid separation, and organic solvent is separated and recovered from liquid phase, which is recycled；Isolated electrolyte and binder from the remaining liquid phase after recycling organic solvent；Isolated active principle aluminium, iron, copper and positive powder from the solid phase after separation of solid and liquid.The method of the present invention simplifies the complicated pre-selection process in Battery disposal process, and disposable efficient process waste and old lithium ion battery improves recovery efficiency, has the characteristics that at low cost, efficient, without secondary pollution.
Description
Technical field
The invention belongs to recycling of WEEE utilize and circular economy technical field, be related to a kind of waste and old lithium ion battery
Recovery method more particularly to it is a kind of based on wet type be crushed waste and old lithium ion battery recovery and treatment method.
Background technique
The problems such as with energy crisis and environmental pollution, becomes increasingly conspicuous, Sustainable Development new energy, construction green
Environmentally friendly low-carbon type society becomes the task of top priority.The cleanings such as lithium ion battery, solar battery, fuel cell and wind-power electricity generation can be again
The raw energy becomes the developing direction of future source of energy, and with the high speed development of electric car industry, lithium ion battery is by its ratio
The unique advantages such as energy is high, small in size, light weight, wide temperature range, production and demand are growing day by day in recent years.
The extensive utilization of lithium ion battery, has not only brought convenience, and the following discarding amount also increases year by year.
The mineral resources in China are relatively fewer, and have many valuable metals such as lithium, cobalt, manganese, nickel, aluminium, copper in waste and old lithium ion battery
Resource, main component include cobaltosic oxide, nickel, cobalt and manganese oxide, nickel cobalt manganese hydroxide, cobalt acid lithium, LiMn2O4, lithium cobalt manganese
Sour lithium.Compared to mineral resources, waste and old lithium ion battery metal resource content is relatively high, and type and content determines, if energy
Metal in high efficiente callback waste and old lithium ion battery and its production waste material, can not only reduce the consumption of mineral resources, additionally it is possible to
Its harm to environment and the mankind is reduced, the industrial upgrading of lithium ion battery is promoted.
Currently, the resource recycle method for lithium ion battery mainly includes hydrometallurgy, pyrometallurgy and biological smelting
Gold.Since lithium ion battery structure includes plastics package, metal shell, positive plate, negative electrode tab and electrolyte, generally adopted in industry
Mode burn off electrolyte and plastic shell, binder for being calcined with pyrogenic process etc., cause treatment process exhaust emission serious.For electricity
The recycling of metal resource in pond, although wet process can utilize the chemical reagent such as sodium hydroxide, sulfuric acid, hydrochloric acid, nitric acid, hydrogen peroxide
The metal ions such as aluminium, nickel, cobalt, manganese, iron, copper, lithium in lithium ion battery are leached, and net by the modes such as precipitating, extracting
Change, separate each metal, but generally can lead to secondary environmental pollution because of the presence of strong acid, highly basic.
CN104577249A discloses a kind of method of resource of waste and old cobalt acid lithium battery, this method is broken using punching machine,
The techniques such as vibrosieve, magnetic separation, vortex electric separation, the roasting of anaerobic normal pressure, alternating temperature filtering, which combine, to be realized in waste and old lithium ion battery
The complete resource of valuable component, and obtain that there are the thick cobalt of the simple substance of high added value, lithium carbonate, graphite, copper, aluminium, iron, plastics etc.
Product.However, being only the roasting of anaerobic normal pressure to the processing mode of the electrolyte in battery in this mode, it is thus possible to cause to give up
Gas pollution.
CN102009054A discloses a kind of waste and old lithium ion battery efficient pulverizing new process, and the technique is by more than release
Electricity, wet type are broken, sieving technology forms, and the efficient pulverizing and selective molecular attraction for realizing waste and old lithium ion battery reduce cobalt acid
The cost recovery of lithium.However, this processing mode is just for cobalt acid lithium secondary cell, to the nickel cobalt manganese for gradually putting into application now
Acid lithium battery, ferric phosphate lithium cell etc. are simultaneously not suitable for, and in the wet type shattering process for adding water, can not efficiently separate anode
With negative electrode active material and collector, making subsequent metal separation process, there are certain difficulties.
Therefore, it needs to develop a kind of clean technologies that can recycle mixing lithium ion battery at present.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of waste and old lithium ion battery recovery methods, especially
It is to provide a kind of waste and old lithium ion battery recovery method being crushed based on wet type.
In order to achieve that object of the invention, the invention adopts the following technical scheme:
The present invention provides a kind of waste and old lithium ion battery recovery method, and described method includes following steps:
(1) waste and old lithium ion battery carries out discharge treatment；
(2) it carries out wet type to the waste and old lithium ion battery after electric discharge to be crushed, the broken solvent used of the wet type is organic
Solvent；
(3) solidliquid mixture obtained after broken to wet type is separated by solid-liquid separation, and organic solvent is separated and recovered from liquid phase,
The organic solvent return step (2) is recycled；
(4) isolated electrolyte and binder in the remaining liquid phase after recycling organic solvent from step (3)；
(5) mixing of isolated active principle aluminium, iron, copper and positive powder in the solid phase after being separated by solid-liquid separation from step (3)
Object.
In the method for the invention, the waste and old lithium ion battery after electric discharge use when wet type is broken organic
Solvent, the wet type carried out using organic solvent is broken, and actually one dissolution is crushed integrated coupling chemistry-physics mistake
The physics shattering process that journey and traditional dry-type pulverizing plus Water type are crushed is entirely different.It is crushed compared to using water as wet type
Solvent, organic solvent can while broken, by dissolve organic binder, thus accelerate separation anode, negative electrode active
Substance and corresponding collector shorten the broken time, improve the separative efficiency of positive and negative electrode material.In broken particle, greatly
The various substances such as partial positive electrode, negative electrode material, aluminium foil are separated to be opened, and dispersion is in organic solvent.Conventional dry, Yi Shui
It fragmentates for broken only battery physics is crushed of wet type of solvent, the various battery materials such as most of anode, cathode are still logical
Binder is crossed to stick together.Meanwhile the organic volatiles such as electrolyte, binder in shattering process will form vapor phase contaminants,
Organic matter degradation by-product caused by after especially fluorine-containing electrolyte, broken blade frictional heat generation is more toxic.By having
The wet type of solvent is broken, and organic vapors pollutant can be absorbed, and reduces secondary pollution in treatment process.Raising separative efficiency,
The broken time is reduced, the damage in shattering process to equipment can also be reduced, extend the service life of equipment.
In the present invention, the active material in the positive electrode of lithium ion battery is LiFePO4, nickel-based oxide, cobalt-based
The combination of one or more of oxide or manganese-base oxide.
Preferably, the active material in the positive electrode of the waste and old lithium ion battery is cobalt acid lithium, lithium nickelate, mangaic acid
One of lithium, binary composite positive pole or ternary composite cathode material or at least two combination.
Preferably, the binary composite positive pole is LiNixCo1–xO2、LiNixMn1–xO2Or LiCo1–xMnxO2In one
Kind or at least two combination, wherein 0≤x≤1.
Preferably, the ternary composite cathode material is LiNixCoyMnl–x–yO2And/or LiNixCoyAll–x–yO2, wherein
0≤x≤1,0≤y≤1, and 0≤x+y≤1.
In the present invention, step (1) discharge treatment is that waste and old lithium ion battery is dipped in salting liquid to put
Electric treatment.
Preferably, the concentration of the salting liquid be 0.1-20%, such as 0.1%, 1%, 3%, 5%, 7%, 8%, 9%,
10%, 12%, 14%, 16%, 18% or 20%, the preferably salting liquid of 1-8%.
Preferably, the salting liquid is NaCl, KCl, NH4Cl、Na2SO4、(NH4)2SO4One or both of combination.
Preferably, the soaking temperature be 10-60 DEG C, such as 10 DEG C, 13 DEG C, 15 DEG C, 18 DEG C, 20 DEG C, 25 DEG C, 30 DEG C,
35 DEG C, 40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C or 60 DEG C.
Preferably, the soaking time be 1-72h, such as 1h, 3h, 5h, 8h, 10h, 15h, 18h, 20h, for 24 hours, 28h,
30h, 33h, 36h, 38h, 40h, 45h, 48h, 50h, 55h, 58h, 60h, 64h, 68h, 70h or 72h, preferably 1-10h.
Preferably, waste and old lithium ion battery is dipped to liquid-solid ratio when carrying out discharge treatment in salting liquid is 0.1-
100L/kg, 0.1L/kg, 1L/kg, 5L/kg, 8L/kg, 10L/kg, 15L/kg, 18L/kg, 20L/kg, 25L/kg, 30L/kg,
35L/kg, 40L/kg, 50L/kg, 60L/kg, 70L/kg, 80L/kg, 90L/kg or 100L/kg.
Preferably, step (2) organic solvent is ketone, arene, fat hydrocarbon, alicyclic hydrocarbon type, alcohols, ether
In class, esters, diol, derivatives or halogenated carboxylic acid any one or at least two combination.
Preferably, the broken used equipment of step (2) wet type is shear crusher, cone crusher, jaw
In formula crusher, hammer mill or impact crusher any one or at least two combination.
Preferably, step (2) the wet type broken time is 0.5-100h, for example, 0.5h, 1h, 3h, 5h, 10h, 15h,
20h, for 24 hours, 28h, 30h, 32h, 36h, 40h, 45h, 48h, 52h, 58h, 60h, 64h, 72h, 80h, 84h, 90h, 96h or
100h, preferably 1-20h.
Preferably, solid-to-liquid ratio when step (2) wet type is broken is more than or equal to 0.1kg/L, such as 0.1L/kg, 1L/
kg、5L/kg、8L/kg、10L/kg、15L/kg、18L/kg、20L/kg、25L/kg、30L/kg、35L/kg、40L/kg、50L/
Kg, 60L/kg, 70L/kg, 80L/kg, 90L/kg or 100L/kg, preferably 0.5-50kg/L.
Preferably, it is 10-200 mesh, such as 10 mesh, 20 mesh, 30 that step (2) wet type, which is crushed the granularity of obtained solid,
Mesh, 40 mesh, 50 mesh, 60 mesh, 70 mesh, 80 mesh, 90 mesh, 100 mesh, 120 mesh, 140 mesh, 160 mesh, 180 mesh or 200 mesh, preferably 50-
100 mesh.
Preferably, the method for step (3) the recycling organic solvent is rectifying, extraction, stripping, absorption, crystallization or film point
From in any one or at least two combination.
Preferably, the method for step (4) the isolated electrolyte and binder is distillation, UF membrane, absorption, extraction
Centrifuge separation in any one or at least two combination.
Preferably, the method for the mixture of step (5) the isolated active principle aluminium, iron, copper and positive powder is attached most importance to
In power separating method, magnetic method, floatation, sieve method or cyclonic separation any one or at least two combination.
Preferably, the exhaust gas return step (2) generated after step (5) described separation is recycled as regenerated solvent.Institute
Stating exhaust gas is the liquid component evaporated when being separated by solid-liquid separation, containing organic solvent and micro electrolyte and conductive agent,
Therefore, it can be used as regenerated solvent and return step (2) is recycled.
As optimal technical scheme, the waste and old lithium ion battery recovery method of the present invention being crushed based on wet type is specifically wrapped
Include following steps:
(1) waste and old lithium ion battery is impregnated into 1-72h, soaking temperature 10- in the salting liquid that concentration is 0.1-20%
60 DEG C, discharge treatment is carried out, liquid-solid ratio when carrying out discharge treatment is 0.1-100L/kg；
(2) it carries out wet type to the waste and old lithium ion battery after electric discharge to be crushed, the broken solvent used of the wet type is organic
Solvent, the wet type broken time are 0.5-100h, and solid-to-liquid ratio when wet type is broken is more than or equal to 0.1kg/L, and wet type is broken
The granularity of obtained solid is 10-200 mesh；
(3) solidliquid mixture obtained after broken to wet type is separated by solid-liquid separation, and organic solvent is separated and recovered from liquid phase,
The organic solvent return step (2) is recycled；
(4) isolated electrolyte and binder in the remaining liquid phase after recycling organic solvent from step (3)；
(5) mixing of isolated active principle aluminium, iron, copper and positive powder in the solid phase after being separated by solid-liquid separation from step (3)
Object, the exhaust gas return step (2) generated after step (5) described separation are recycled as regenerated solvent.
Compared with the existing technology, the invention has the following advantages:
The solvent that the present invention is crushed using organic matter as wet type, can be living by dissolution binder separation anode, cathode
Property substance and corresponding collector, shorten process flow；Waste and old lithium ion battery collaboration is handled, is simplified in Battery disposal
The complicated pre-selection process of process, disposable efficient process waste and old lithium ion battery improve recovery efficiency；Made using organic matter
For the solvent that wet type is crushed, the damage in shattering process to equipment can be reduced, the service life of equipment is extended.In addition, this hair
It is bright by wet type is broken cooperate other separate modes such as rectifying separation, solid sorting etc. in the way of combine realize waste and old lithium from
The separation of the valuable component of sub- battery, so that wherein for the rate of recovery of metal 98% or more, organic solvent can be with closed cycle benefit
With compared with the separation methods such as inorganic Ore Leaching, extraction and separation, chemical precipitation, at low cost, efficient, without secondary pollution etc.
Feature.
Detailed description of the invention
Fig. 1 is process flow chart of the present invention for waste and old lithium ion battery recycling.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
In the present embodiment, waste and old lithium ion battery recycling is carried out by the following method, specifically includes following steps (its work
Skill process is as shown in Figure 1):
(1) waste and old lithium ion battery to be processed is impregnated into 2h in 5% sodium chloride solution, the active matter in positive electrode
Matter is nickel-based oxide, cobalt base oxide, manganese-base oxide, and soaking temperature is 25 DEG C, liquid-solid ratio 2L/kg, applying waste lithium ionic
The remaining electric Spontaneous release of battery；
(2) by after electric discharge waste and old lithium ion battery and organic solvent N-Methyl pyrrolidone (NMP) mix, shearing
It is broken that wet type is carried out in crusher, being crushed the time is 2h, solid-to-liquid ratio 3kg/L, and the particle size range for being crushed obtained solid is 50-
100 mesh；
(3) solidliquid mixture obtained after broken to wet type is separated by solid-liquid separation, and obtained liquid phase is separated in a manner of rectifying
Organic solvent recycles the organic solvent return step (2)；
(4) residual solution after step (3) to be recycled to organic solvent mutually passes through distillation and efficiently separates, isolated electrolysis
The mixture of liquid and binder；
(5) solid phase after being separated by solid-liquid separation step (3) after drying, using gravity separation separate aluminium therein, iron,
The mixture of copper, positive powder, the exhaust gas return step (2) generated after step (5) described separation make as regenerated solvent circulation
With.
The rate of recovery of each metal recycled from waste and old sub- battery through this embodiment is shown in Table 1.
Table 1
| Metal | Al | Fe | Cu |
| The rate of recovery | 99.31% | 99.85% | 99.82% |
Embodiment 2
In the present embodiment, waste and old lithium ion battery recycling is carried out by the following method, specifically includes following steps (its work
Skill process is as shown in Figure 1):
(1) waste and old lithium ion battery to be processed is impregnated into 72h in the solution of 0.1% ammonium chloride and potassium chloride, anode
Active material in material is LiFePO4, and soaking temperature is 60 DEG C, liquid-solid ratio 0.1L/kg, waste and old lithium ion battery it is remaining
Electric Spontaneous release.
(2) waste and old lithium ion battery after electric discharge is mixed with the mixture of trifluoroacetic acid and dimethylbenzene, is successively being impacted
It is broken that wet type is carried out in formula crusher and jaw crusher, being crushed the time is 0.5h, solid-to-liquid ratio 0.1kg/L, and it is solid to be crushed gained
The particle size range of body is 50-100 mesh.
(3) solidliquid mixture obtained after broken to wet type is separated by solid-liquid separation, and obtained liquid phase is separated in a manner of rectifying
Organic solvent recycles the organic solvent return step (2)；
(4) residual solution after step (3) to be recycled to organic solvent mutually passes through distillation and efficiently separates, isolated electrolysis
The mixture of liquid and binder；
(5) solid phase after being separated by solid-liquid separation step (3) after drying, using gravity separation separate aluminium therein, iron,
The mixture of copper, positive powder, the exhaust gas return step (2) generated after step (5) described separation make as regenerated solvent circulation
With.
The rate of recovery of each metal recycled from waste and old sub- battery through this embodiment is shown in Table 2.
Table 2
| Metal | Al | Fe | Cu |
| The rate of recovery | 99.23% | 99.96% | 98.39% |
Embodiment 3
In the present embodiment, waste and old lithium ion battery recycling is carried out by the following method, specifically includes following steps (its work
Skill process is as shown in Figure 1):
(1) waste and old lithium ion battery to be processed is impregnated into 1h, positive material in the solution of 20% sodium sulphate and ammonium sulfate
Active material in material is LiFePO4, and soaking temperature is 10 DEG C, liquid-solid ratio 100L/kg, the remaining electricity of waste and old lithium ion battery
Spontaneous release；
(2) waste and old after being put into electric discharge after by hexamethylene, ethyl acetate and ethylene glycol with the mixing of volume fraction 1:1:1
Lithium ion battery successively carries out wet type in cone crusher and hammer mill and is crushed, and being crushed the time is 20h, solid-to-liquid ratio
For 50kg/L, the particle size range for being crushed obtained solid is 50-100 mesh；
(3) solidliquid mixture obtained after broken to wet type is separated by solid-liquid separation, and obtained liquid phase is separated in a manner of rectifying
Organic solvent recycles the organic solvent return step (2)；
(4) residual solution after step (3) to be recycled to organic solvent mutually passes through distillation and efficiently separates, isolated electrolysis
The mixture of liquid and binder；
(5) solid phase after being separated by solid-liquid separation step (3) after drying, using gravity separation separate aluminium therein, iron,
The mixture of copper, positive powder, the exhaust gas return step (2) generated after step (5) described separation make as regenerated solvent circulation
With.
The rate of recovery of each metal recycled from waste and old sub- battery through this embodiment is shown in Table 3.
Table 3
| Metal | Al | Fe | Cu |
| The rate of recovery | 99.56% | 99.79% | 98.22% |
Embodiment 4
In the present embodiment, waste and old lithium ion battery recycling is carried out by the following method, specifically includes following steps (its work
Skill process is as shown in Figure 1):
(1) waste and old lithium ion battery to be processed is impregnated into 1h in the solution of 10% sodium sulphate, the work in positive electrode
Property substance be nickle cobalt lithium manganate (LiNi1/3Co1/3Mn1/3O2) and LiFePO4, soaking temperature is 10 DEG C, liquid-solid ratio 100L/
Kg, the remaining electric Spontaneous release of waste and old lithium ion battery；
(2) waste and old after being put into electric discharge after by dimethyl ether, propyl alcohol and 2- glycol chlorohydrin with the mixing of volume fraction 1:1:1
Lithium ion battery successively carries out wet type in cone crusher and shear crusher and is crushed, and being crushed the time is 1h, solid-to-liquid ratio
For 20kg/L；The particle size range of broken obtained solid is 50-100 mesh；
(3) solidliquid mixture obtained after broken to wet type is separated by solid-liquid separation, and obtained liquid phase is separated in a manner of rectifying
Organic solvent recycles the organic solvent return step (2)；
(4) residual solution after step (3) to be recycled to organic solvent mutually passes through distillation and efficiently separates, isolated electrolysis
The mixture of liquid and binder；
(5) solid phase after being separated by solid-liquid separation step (3) after drying, using gravity separation separate aluminium therein, iron,
The mixture of copper, positive powder, the exhaust gas return step (2) generated after step (5) described separation make as regenerated solvent circulation
With.
The rate of recovery of each metal recycled from waste and old sub- battery through this embodiment is shown in Table 4.
Table 4
| Metal | Al | Fe | Cu |
| The rate of recovery | 99.45% | 99.26% | 99.80% |
By being the broken solvent of wet type using organic matter, waste and old mixing lithium ion battery is recycled, is separated
Obtained aluminium, iron, copper the rate of recovery be more than 99%, the organic solvent cycling rate for the treatment of process is more than 97%, is effectively kept away
Exempt from secondary pollution of the organic solvent to environment, while also reducing production cost.
The Applicant declares that the present invention illustrates the process method of the present invention through the above embodiments, but the present invention not office
It is limited to above-mentioned processing step, that is, does not mean that the present invention must rely on the above process steps to be carried out.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to raw material selected by the present invention
Addition, selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (23)
1. a kind of waste and old lithium ion battery recovery method, which is characterized in that described method includes following steps:
(1) waste and old lithium ion battery carries out discharge treatment；
(2) it carries out wet type to the waste and old lithium ion battery after electric discharge to be crushed, the broken solvent used of the wet type is organic solvent；
(3) solidliquid mixture obtained after broken to wet type is separated by solid-liquid separation, and organic solvent is separated and recovered from liquid phase, by this
Organic solvent return step (2) recycles；
(4) isolated electrolyte and binder in the remaining liquid phase after recycling organic solvent from step (3)；
(5) mixture of isolated active principle aluminium, iron, copper and positive powder in the solid phase after being separated by solid-liquid separation from step (3).
2. the method according to claim 1, wherein the activity in the positive electrode of the waste and old lithium ion battery
Substance is one of cobalt acid lithium, lithium nickelate, LiMn2O4, binary composite positive pole or ternary composite cathode material or at least two
The combination of kind.
3. according to the method described in claim 2, it is characterized in that, the binary composite positive pole is LiNixCo1–xO2、
LiNixMn1–xO2Or LiCo1–xMnxO2One of or at least two combination, wherein 0 < x < 1.
4. according to the method described in claim 2, it is characterized in that, the ternary composite cathode material is LiNixCoyMnl–x–yO2
And/or LiNixCoyAll–x–yO2, wherein 0 < x <, 1,0 < y < 1, and 0 < x+y < 1.
5. the method according to claim 1, wherein step (1) discharge treatment is by applying waste lithium ionic electricity
Pond, which is dipped in salting liquid, carries out discharge treatment.
6. according to the method described in claim 5, it is characterized in that, the concentration of the salting liquid is 0.1-20%.
7. according to the method described in claim 6, it is characterized in that, the concentration of the salting liquid is 1-8%.
8. according to the method described in claim 5, it is characterized in that, the salting liquid is NaCl, KCl, NH4Cl、Na2SO4、
(NH4)2SO4In any one or at least two combination.
9. according to the method described in claim 5, it is characterized in that, the soaking temperature is 10-60 DEG C.
10. according to the method described in claim 5, it is characterized in that, the soaking time is 1-72h.
11. according to the method described in claim 5, being carried out it is characterized in that, waste and old lithium ion battery is dipped in salting liquid
Liquid-solid ratio when discharge treatment is 0.1-100L/kg.
12. the method according to claim 1, wherein step (2) organic solvent be ketone, arene,
Any one in fat hydrocarbon, alicyclic hydrocarbon type, alcohols, ethers, esters, diol, derivatives or halogenated carboxylic acid or at least two
Combination.
13. the method according to claim 1, wherein equipment used in step (2) wet type is broken is to cut
In cut type crusher, cone crusher, jaw crusher, hammer mill or impact crusher any one or at least
Two kinds of combination.
14. the method according to claim 1, wherein the time that step (2) wet type is crushed is 0.5-
100h。
15. according to the method for claim 14, which is characterized in that step (2) the wet type broken time is 1-20h.
16. the method according to claim 1, wherein solid-to-liquid ratio when step (2) wet type is broken is greater than etc.
In 0.1kg/L.
17. according to the method for claim 16, which is characterized in that solid-to-liquid ratio when step (2) wet type is broken is
0.5-50kg/L。
18. the method according to claim 1, wherein the granularity that step (2) wet type is crushed obtained solid is
10-200 mesh.
19. the method according to claim 1, wherein the method for step (3) the recycling organic solvent is essence
Evaporate, extract, in stripping, absorption, crystallization or UF membrane any one or at least two combination.
20. the method according to claim 1, wherein step (4) the isolated electrolyte and binder
Method is the combination of any one or at least two in distillation, UF membrane, absorption, extraction or centrifuge separation.
21. the method according to claim 1, wherein step (5) the isolated active principle aluminium, iron, copper
Method with the mixture of positive powder is any one in gravity separating method, magnetic method, floatation, sieve method or cyclonic separation
Or at least two combination.
22. the method according to claim 1, wherein the exhaust gas return step generated after step (5) described separation
(2), it is recycled as regenerated solvent.
23. method described in any one of -22 according to claim 1, which is characterized in that the described method comprises the following steps:
(1) waste and old lithium ion battery being impregnated into 1-72h in the salting liquid that concentration is 0.1-20%, soaking temperature is 10-60 DEG C,
Discharge treatment is carried out, liquid-solid ratio when carrying out discharge treatment is 0.1-100L/kg；
(2) wet type being carried out to the waste and old lithium ion battery after electric discharge to be crushed, the broken solvent used of the wet type is organic solvent,
The wet type broken time is 0.5-100h, and solid-to-liquid ratio when wet type is broken is more than or equal to 0.1kg/L, and the broken gained of wet type is solid
The granularity of body is 10-200 mesh；
(3) solidliquid mixture obtained after broken to wet type is separated by solid-liquid separation, and organic solvent is separated and recovered from liquid phase, by this
Organic solvent return step (2) recycles；
(4) isolated electrolyte and binder in the remaining liquid phase after recycling organic solvent from step (3)；
(5) mixture of isolated active principle aluminium, iron, copper and positive powder in the solid phase after being separated by solid-liquid separation from step (3), step
Suddenly the exhaust gas return step (2) generated after (5) described separation is recycled as regenerated solvent.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610214115.XA CN107275700B (en) | 2016-04-07 | 2016-04-07 | A kind of waste and old lithium ion battery recovery and treatment method being crushed based on wet type |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610214115.XA CN107275700B (en) | 2016-04-07 | 2016-04-07 | A kind of waste and old lithium ion battery recovery and treatment method being crushed based on wet type |
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| Publication Number | Publication Date |
|---|---|
| CN107275700A CN107275700A (en) | 2017-10-20 |
| CN107275700B true CN107275700B (en) | 2019-07-05 |
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| EP4118704A4 (en) * | 2020-06-17 | 2024-05-15 | Grst Int Ltd | Method for composite delamination |
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